Antistatic acylhydrazinium salt



Claims priority, application Japan, July 7, 1967,

42/ 43,324 Int. Cl. G03c 5/26 US. Cl. 9650 3 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive silver halide photographic material containing an acylhydrazinium salt used as an anti-static agent.

This invention relates to light-sensitive silver halide photographic materials characterized in that the constitutive elements of light-sensitive silver halide photographic materials are incorporated with acylhydrazinium salts represented by the general formula shown later.

A principal object of the present invention is to provide light-sensitive silver halide photographic materials less in drawbacks due to electrostatic charge.

Another object is to provide light-sensitive black and white photographic materials improved in tone of developed silver image, and light-sensitive color photographic materials excellent in image resolution and graininess.

When light-sensitive silver halide photographic materials have been developed, there are some cases where undesired images in the form of branches or fluffs are frequently observed. These images are so-called static marks, and it is said that the generation of static marks is ascribable to the discharge of surface charge produced by friction. The drawbacks due to such electrostatic charge not only result in the formation of static marks but also bring about the adhesion of dust onto the surfaces of light-sensitive materials. Such electrostatic drawbacks necessarily take place, in general, in the cases where light-sensitive materials are subject to friction, throughout substantially all the stages of production and handling of light-sensitive materials. For example, said drawbacks are brought about in such production stages as coating of emulsions, and cutting and packaging of lightsensitive materials; at the time of withdrawing sheet films from boxes; at the time of taking photographs, particularly filming; and at the time of handling prior to development. Further, such electrostatic drawbacks are sometimes observed also in the case where light-sensitive materials are peeled, in addition to the above-mentioned case where they undergo abrasion. For example, after completion of coating and drying, light-sensitive materials are wound up, in general, and, in the case of unwinding said materials in succession in order to, transfer them to the subsequent step or in the case of unrolling rolled printing papers in succession in order to subject them to printing, static charge is generated by peeling between the surface and the reverse side of the lightsensitive material at the moment when it is peeled from the rolled portiton. Further, when a printing paper has United States Patent 0 been subjected to ferrotype drying, release static charge is generated between the metal surface and the surface of the light-sensitive material, at the time when it is peeled, to bring about such a phenomenon that'the superposition of the printing paper cannot be effected immediately.

As a measure of preventing such drawbacks due to electrostatic charge, there has frequently been adopted a process in which hygroscopic substances are incorporated into the constitutive elements of light-sensitive materials. This process, however, is elfective only in the case where humidity is relatively high, and is ineffective at a dry time when electrostatic drawbacks are frequently brought about. Further, in case the humidity is excessively high, said process accompanies such troubles as adhesion between film surfaces of light-sensitive materials. In addition to said moisture absorptive materials, there are a considerable number of compounds known as antistatic agents. In application to light-sensitive materials, however, antistatic agents are required to be such that they should not give any detrimental effect to the photographic characteristics of light-sensitive materials, such as the sensitivity, gradation, fog and stability thereof. It is therefore extremely difiicult to find excellent antistatic agents applicable to light-sensitive silver halide photographic materials.

The present inventors made various studies on excellent antistatic agents having no detrimental effect on lightsensitive silver halide photographic materials. As the result, the inventors have found that compounds represented by the general formula wherein R R and R are individually a lower alkyl group, an aralkyl group, or a group derived therefrom; R is a hydrogen atom or an alkyl group; and X is an anion residue, are excellent antistatic agents.

When the above-mentioned compounds are incorporated into at least one layer of the constitutive elements of light-sensitive silver halide photographic materials, such as silver halide emulsion layer, sublayer, inter layer, filter layer, antihalation layer, protective layer and backing layer, it is possible to obtain light-sensitive silver halide photograhic materials markedly less in electrostatic drawbacks. Further, the incorporation of said compounds not only gives no detrimental effect to the efficiencies of light-sensitive photographic materials, such as sensitivity, gradation, fog and the like, but also has such favorable effects as to inhibit the fog and to increase the stability thereof. When applied to light-sensitive black and white photographic materials, the above-mentioned compounds give such advantages as to bring the color tones of developed silver images to bluish black, in addition to the prevention of electrostatic drawbacks. Further, when applied to incorporated type of color photographic emulsions, the compounds improve the dispersibility of color formers to make it possible to obtain lightsensitive color-photographic materials excellent in image resolution and graininess.

Typical examples of certain acylhydrazinium salts having the aforesaid general formula include those shown in the table below.

Raf

Elementary atnalysis Calculated Found cy1hyrzinium" poroboratesi are obta lnedfelithe ng aym'yd aim tr ti m-tan y; orighiilin fl ioborates in i acylhydraginium chloride with so lEmb es sweet: 375%" 5 ssnqt ia with lgilkyhoearal 6O alutions irr silij tablleso ems such aswater 51505015. A1

by distillation under reduced pressure there'sidueis dis- -375 sasse essssa m solved nil o thelgol utiorl, rill.

f, he 1 1 4, a Whit sql s p e d qflsq l d by; filtration.. The solids are recrystallized,repeatedly from nietheiiol-ther to .;obtai n 33.2 3. 915 1 White .p la tes, MJP. 77 5-71.55 0,, yield. 80%; elementary ar alysis: N,16.86%,

liqr .the. incorporation of. thle comfiourias havihg yaioresaidlge l eral formula, iritosilirer. halide. emulsion fay-' {$9.5 l ayer, inter layer, filter; leyer, ar tihalhtion-glayer, protective layer. and hacking laye rgwhichuere constitutive element's? .ofi light sensitive silver helide photographic, 111a} ter saiicoriijiolinds maybe. addedjin the form of sosq rf aces' of lightrsensitiye photqrziphic meterials' or light? entingfsqlixtion, incorporating the compounds vrnzi te ia lj. I :1 a '1 .Further; the compounds; of the present.invention .are.

qinpblihds areto begqq d bu may. e. sq mm' ued. as f.-0 .1-mg.- 1 g.; per sgpare meterof the light-sensitive applicable to .the static charge prevention of films, molded articles. and fibers of. cellulose esters, polyesters, polystyrenes, polycarbonates, polyethylenes, polypropylenes and the like synthetic resins. i

The following examples illustrate the present invention.

EXAMPLE 1 An aqueous solution containing 1% (CH NNHCOC H Br (exemplified as III) was sprayed onto the surface of a high speed X-ray film, in the amount of 10 mg. per square meter of the film, and the sprayedfilm was then dried to prepare a sample. Further, the same X-ray film as above was immersed for 1 minute in the above-mentioned solution and was then dried to prepare another sample. n the other hand, two control samples were prepared in the same manner as above, except that the treatments were effected by use of pure water containing no said acylhydrazinium compound. After allowing these 4 samples to stand for 24 hours at 25 C. and a relative humidity of 30%, the samples were rubbed on the surfaces with nylon and polyester cloths and were then subjected, without exposure to light, to development according to an ordinary procedure using a developer for X-ray film. On the films treated with pure water, the generation of considerable marked static marks was observed, whereas on the films treated with the solution of acylhydrazinium compound, no generation of static marks was observed.

On the other hand, these 4 kinds of films were subjected to sensitometry according to the procedures regulated in I IS, whereby not only no influence was observed in sensitivity, gradation and fog of the light-sensitive silver halide photographic materials of the present invention but also the color tones of developed silver images changed to bluish black to obtain favorable results. Further, the films were individually stored in a thermostat at 55 C. for 3 days or at 50 C. and 80% RH for 3 days, and were then developed. In this case also, the lightsensitive silver halide photographic materials of the present invention gave favorable results.

EXAMPLE 2 CH3 CHs N NHCOC HnB F2 (exemplified as X) was prepared to a 2% aqueous solution. To a 3% aqueous gelatine solution employed for a protective layer, the above-mentioned solution was added in an amount of cc. per liter of said gelatine solution. The mixed solution was further incorporated with 2 cc. of a 5% saponin solution as a coating aid. The thus prepared solution was applied as a protective layer onto a high speed X-ray film and was then dried. The resulting light-sensitive material was subjected to entirely the same tests as in Example 1, together with a light-sensitive material having a protective layer which had not been incorporated with the above-mentioned compound, whereby the same results as in Example 1 were obtained. 1

EXAMPLE 3 (CHa)2 NGBNHCOCMHMCKMG (exemplified as x1 was prepared to a 3% methanol solution. To a greensensitive high speed color photographic silver iodobromide emulsion, the above-mentioned solution was added in an amount of 30 cc. per liter of said emulsion. This emulsion was then incorporated with a solution prepared by dissolving in a l N-caustic soda solution, g. of 1-(4- carboxyphenyl) 3 (4-palmitoylaminobenzoylamino)- 5-pyrazolone (magenta color former), and the pH of the emulsion was adjusted to 6.8 by means of citric acid. The thus prepared emulsion was applied onto a cellulose triacetate base and was then dried. The resulting film was subjected to entirely the same tests as in Example 1, together with a sample film to which no acylhydrazinium compound had been added. Provided that, in this case, the processing was carried out according to such ordinary procedures that the films were developed by use of a color developer containing diethyl-p-phenylenediamine and were then subjected to water-washing, bleaching, water-washing, fixing, water-washing and drying. As the result, it was recognized that the light-sensitive silver halide photographic material of the present invention had been completely inhibited from the generation of static marks and had been improved in dispersibility of developed dye. Further, the results of incubation test of the films were as set forth in the table below, and it was observed that the light-sensitive material of the present invention had been somewhat improved in stability.

was prepared to a 2% aqueous solution. 3 cc. of this solution was added to cc. of a 7% aqueous gelatine solution containing an antihalation dye. The mixed solution was further added with 3 cc. of a 5% saponin solution. This solution was coated onto a cellulose triacetate film base and was dried. Further, onto the opposite side of said film base, a high speed photographic negative emulsion was applied. Into the protective layer thereof also, the above-mentioned compound had been incorporated in an amount of 100 mg. per liter of said gelatine solution. The resulting light-sensitive material was subjected to entirely the same tests as in Example 1 to recognize that the light-sensitive silver salide photographic material of the present invention had been inhibited from the generation of static marks and no detrimental influence had been given to the sensitivity, gradation, fog and stability of the photographic emulsion.

What is claimed is:

1. A light-sensitive silver halide photographic material characterized by containing in the constitutive elements of the light-sensitive silver halide photographic material, an acylhydrazinium salt represented by the general formula wherein R R and R are individually a lower alkyl group, an aralkyl group or a group derived therefrom; R is a hydrogen atom or an alkyl group; and X is an anion residue.

2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said photographic material is a color photographic material.

3. A process for the treatment of a light-sensitive silver halide photographic material thereby to impart anti- 

